Electroreductive fluoroalkylative heteroarylation of unactivated alkenes via an unconventional remote heteroaryl migration

Perfluoroalkyl-containing organic molecules are important for a wide range of applications in pharmaceuticals and organic functional materials. In this study, an unconventional electroreductive fluoroalkylative heteroarylation of unactivated alkenes via a remote heteroaryl migration is developed. A series of heteroaryls can migrate smoothly, and various fluoroalkyls can be introduced into products. Compared with classical thermochemistry and photochemistry, electrochemistry uses generation of radicals and subsequent radical addition to unactivated alkenes, and heteroaryl migration and hydrogen atom abstraction occur in a small reductive area near the cathode. This approach contributes to the broad substrate scope. Deuterium-labeling experiments and density functional theory calculations indicate that N,N-dimethylformamide provides hydrogen atoms for the quenching of carbon radicals after migration instead of water or tetrabutylammonium hexafluorophosphate. A migrated benzothiazole moiety can be transformed into a formyl group, and a facile synthesis can generate substituted cyclopentanone. [Display omitted] •Electroreductive fluoroalkylative heteroarylation of unactivated alkenes is carried out•A remote heteroaryl migration occurs•Polyfluoroalkylated esters and polyfluoroalkylated cyclopentanone are synthesized•Experiments and DFT calculations give insights into the reaction mechanism Here, Chen et al. report an electroreductive fluoroalkylative heteroarylation of unactivated alkenes, capitalizing on a remote heteroaryl migration. Mechanistic investigations indicate that the desired reaction occurs near the cathode, and hydrogen atoms in the products are derived from N,N-dimethylformamide.